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The present invention relates generally to the production of perovskite products, such as typified by ruthenium-based oxide compounds, and more particularly to their densification and sintering under high-pressure conditions.
Simple ruthenium based oxides, for example, ARuO3, where A is Sr, Ba, or Ca, have interesting magnetic and electrical properties. These oxides also have the potential for device applications. SrRuO3, for example, is a ferromagnet with Tcxcx9c160 K, whereas CaRuO3 exhibits no ferromagnetic order. These ruthenium-based oxides also are electrically conductive.
SrRuO3, for example, has commercial application as a high density sputtering target for a variety of emerging electronic applications including, for example, production of thin films as electrodes in the next generation of high capacity stack storage capacitors and production of dynamic random access memory (DRAM) and ferroelectric random access memory (FeRAM) for the semiconductor industry. The theoretical density of SrRuO3 is 6.489 g/cc. SrRuO3 targets with high density ( greater than 90% of theoretical density) are essential for production of thin films with uniform thickness by sputtering. SrRuO3, however, is difficult to densify by conventional methods, such as cold pressing and sintering, or hot pressing. Sintering temperatures also are limited to less than 1400xc2x0 C. due to dissociation of the compound at low pressures and contamination because of reaction with containment material. SrRuO3 compacts made by conventional densification methods are reported to have densities of less than 50% of the theoretical density.
Thus, there exists a need in the art to provide dense compacts of cubic perovskite products, as typified by ruthenium-based oxides.
A perovskite feedstock (e.g., a perform or powder) is placed in a high=pressure cell of a high pressure/high temperature (HP/HT) apparatus and subjected to pressures in excess of about 2 kbar and temperatures above about 800xc2x0 C. for a time adequate to increase the density of the perform. The perform may be made, interalia, by cold pressing, cold pressing and sintering, or hot pressing.
High pressure and high temperature processing of cubic perovskite preforms has an advantage in sintering of the preforms to higher densities. Another advantage is that high pressure may accomplish the sintering at lower temperatures, thus preserving stoichiometric and purity. A further advantage is that sintering at higher temperatures can be done without dissociation of the compound. Further sintering at high pressures will minimize grain growth so that fine-grained dense compacts can be produced. Fine grain size and high density are very important for targets used in production of thin films with uniform thickness. These and other advantages will be readily apparent to those skilled in the art based upon the present disclosure.
SrRuO3 belongs to class of materials called cubic perovskites. The principle perovskite structure found in ferroelectric materials is a simple cubic structure containing three different ions of the form ABO3. The A and B atoms represent +2 and +4 ions, respectively, while the O atom is the Oxe2x88x922 ion. This ABO3 structure, in a general sense, can be thought of as face centered cubic (FCC) lattice with A atoms at the corners and the O atoms on the faces. The B atom completes the picture and is located at the center of the lattice. This A atom is the largest of the atoms and consequently increases the overall size of the AO3 (FCC) structure. As a result, there are minimum energy positions off centered from the original octahedron that can be occupied by the B atom.
Different types of A and B elements include:
Dodecahedral A-site: Na+, K+, Rb+, Ag+, Ca+2, Sr+2, Ba+2, Pb+2, La+3, Pr+3, Nb+3, Bi+3, Y+3, Ce+4, Th+4.
Octahedral B-site: Li+, Cu+2, Mg+2, Ti+3, V+3, Cr+3, Mn+3, Fe+3, Co+3, Al+3, Ni+3, Rh+3, Hf+4, Ti+4, Zr+4, Mn+4, Ru+4, Pt+4, Nb+5, Ta+5, Mo+6, W+6.
The atomic structure of ferroelectric thin films is very sensitive to fluctuations in the temperature of the crystal. As the temperature is changed, the crystallographic dimensions change due to distortion of the octrahedra. These different crystal structures are: cubic, tetragonal, orthorhombic, and rhombohedral. As a result, the distorted octrahedra are coupled together, and a very large spontaneous polarization can be achieved. This large spontaneous polarization will lead to a large dielectric constant, with sensitive temperature dependence.
Reported applications of perovskites include: BaTiO3, multilayer capacitor; Pb(Zr, Yi)O3, piezoelectric transducer; BaTiO3; electro-optic modulator, (Pb, La)(Zr, Ti)O3; LiNbO3, switch; BaZrO3, dielectric resonator; BaRuO3, thick film resistor; Pb(Mg, Nb)O3, electrostrictive actuator; Ba(Pb, Bi)O3 layered cuprates, superconductor; GdFeO3, magnetic bubble memory; YAlO3, laser host; (Ca, La)MnO3, refractory electrode; and KNbO3, second harmonic generator. While most perovskites have high electrical resistivities that make them good as dielectrics, some are considered to be good conductors and semi-conductors. Some of the best perovskite conductors are the cubic sodium tungsten bronzes (NaxWO3; where x is between 0.3 and 0.95). In these bronzes, the resistivity tends to minimize at 0.7 mole-% of Na.
The perovskite material subjected to the HP densification process, or feedstock, can be in powder form or can be converted into a preform for ease in handling. A xe2x80x9cpreformxe2x80x9d is a coherent mass of material in a pre-determined shape. The preform most often is made by pressing of the feed material, optionally, with heat added during the pressing or afterwards (sintering). Regardless of the technique of choice in forming the preform, such preform (or the powder itself) next is placed within a shield or enclosure material (Ta, Grafoil) and the wrapped preform placed within the reaction cell of the HP/HT apparatus.
The basic high pressure/high temperature (HP/HT) manufacturing method of the type herein involved entails the placing of a mass of feed cubic perovskite within a protectively shielded enclosure which is disposed within the reaction cell of an HP/HT apparatus of a type described in U.S. Pat. Nos. 2,947,611; 2,941,241; 2,941,248; 3,609,818; 3,767,371; 4,289,503; 4,673,414; and 4,954,139. The contents of the cell then are subject to processing conditions selected as sufficient to affect a sintering and densification of the cubic perovskite. Such processing conditions generally involve the imposition of a pressure above about 2 kbar and temperatures above about 800xc2x0 C. for at least about 3 minutes. Useful pressure can be expected to range from about 2 to about 75 kbar with corresponding useful temperatures from between about 800xc2x0 to about 1600xc2x0 C. Pressing times should ranges from about 3 minutes to about 24 hours.
Following such high-pressure excursion, the temperature initially is lowered followed by release of the pressure. The shield material then can be ground off or dissolved in a solvent therefor and the densified cubic perovskite recovered. The densified cubic perovskite then can be machined or otherwise processed according to its intended use.
While the invention has been described with reference to a preferred embodiment, those skilled in the art will understand that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed as the best mode contemplated for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. In this application all units are in the metric system and all amounts and percentages are by weight, unless otherwise expressly indicated. Also, all citations referred herein are expressly incorporated herein by reference.